CALCIUM CARBONATE SATURATION IN SEAWATER: EFFECTS OF DISSOLVED ORGANIC MATTER Keith E.

Chase and Erwin Suess2

Hawaii Institute of Geophysics and Department of Oceanography, University of Hawaii, Honolulu 96822
ABSTBACI

Surface seawater is generally supersaturated with CaCOs; but carbonate will not prcdpitate from natural seawater in convenient experimental times. If the supersaturation is increased by the addition of Ca2 or C03- ions, precipitation can occur in minutes or hours. Seawater, with 0.1 m Na&Os solution added to give a pH of 9.5, will begin rapid CaCOs (aragonite) precipitation in as little as 15 min. The length of time between the addition of the N&CO3 and rapid precipitation increases with an increase in the dissolved organic content of the water. If CaCL, which produces no pI1 increase, is added to seawater, CaSOc.21140 (gypsum) is the only precipitate that will form within 12 hr.
INTRODUClTON

CaC03

The supersaturation of CaC03 in surface seawater was first noted in the central AtEXPERIMENTS lantic by Wattenberg and Timmerman Calcium carbonate will not precipitate ( 1936). Others have since observed this from naturally occurring supersaturated phenomenon in many widely scattered surface seawater in reasonable experimenareas (e.g., Cloud 1962; McIntyre and tal times, Thus, to study rates of nucleaPlatford 1964; Pytkowicz and Fowler 1967; tion, it is necessary to increase the degree Lyakin 1968). It appears that most surface of supersaturation artificially. This is easwaters of the worlds oceans are supersatuily accomplished by the addition of Ca+ rated. This disequilibrium state of the or COs2- ions. If these are added in the CaC03 system in surface seawater has form. of CaCl2 or Na&On solutions,, the generally been attributed to some nonspe- gross chemistry of the seawater changes cific, inorganic reaction kinetic control. On little since Na- and Cl- are the dominant the basis of laboratory experiments, Pyt- ions of seawater. kowicz (1965) showed the effect of magnesium in solution in seawater in the regulation of carbonate nucleation kinetics. Natural seawaters from a variety of enSimkiss (1964) has shown that dissolved vironments around Hawaii were passed phosphorus compounds inhibit CaC03 pre- through 0.8-p Millipore filters and continuously stirred. Portions ( 160 ml) of the cipitation. Chave ( 1965) and Chave and Suess filtrates were brought to pH 9.5 by addition of 0.1 m Na2C03 solutions. The ( 1967) suggested that naturally occurring solution required to organic compounds inhibited reactions be- amount of Na&03 tween carbonate minerals and seawater. reach this pH ranged, with one exception, from 5.7-6.7 ml; about 0.6 mmoles of C032This report presents the results of experiper sample was added. ments to determine the effect of dissolved organic compounds on the nucleation of 3 To approximate a consistent degree of super1 This work was supported by Office of Naval Research Contract NR 083-194. Contribution 374 from the Hawaii Institute of Geophysics. 2 Present address: Geologisch-Palaontologischcs Institut der Universitgt, 23 Kiel, Olshausenstrassc 40/60, West Germany. saturation by addition of Na2COs to various seawaters, the choice of adding a constant amount of NaEOs, or of adding NaE03 to a constant pH, is arbitrary. Because of the disequilibrium in either system, it is impossible to describe the absolute supersaturation. Addition of NazCOa to a constant pH was chosen for these experiments.

from filtered seawatcrs.

natural

and artificial

633

634
9.5 9.4 ---A:+,, . Y=c \;---*---.+. \ .

KEIII-I

E.

CHAVE

AND

ERWlN

SUES3

TAIHX -.

1.

Effect

CaCOs precipitation
3.0 mGC/L

of dissolved organic carbon. on from seawater raised to

pH 9.5
0.1 m Na,C08 added/ Initial j?II
Time to

9.3 1

?\ .

\ Scawnter sample

Dissolved org-C

rnpid pII de-

9.0

I IO

, 20

I 30 TIME,

I 40
MIN

1 50

I 60

I 70

PIG. 1. Change in VI-I with time after addition of NanCOs solutions. Rapid precipitation of CaCO:, is indicated by a rapid decrease in pII. Dissolved organic carbon (mg C/liter ) of each sample is indicated.

Plots of pII change with time after the addition of Na&08, Eor three typical expcrimcnts, arc shown in Fig. i.- In the Lxpcrimcnts, the $1 dccrca&s slowly at first and then rapidly as a thick white precipitate of CaCOs (aragonite) is formed. Total dissolved o,rganic carbon was dctermined on each of-the filtered seawater samples bcforc the prccipita tion expcriments, using the method of Menzel and Vaccaro ( 1964). The length of time bctween the addition of Na2CO:I and the rapid precipitation of carbonate, as indicated by a rapid pH dccrcasc, appears to be related to the dissolved organic content of the water (Fig. 1, Table 1). Two samples of scawatcr from laboratory aquaria, with unusually high dissollved organic contents, did not precipitate CaCOs in 3 to 4 hr after additions of Na&03. The longer experiments were not continued bccausc WC:felt that after this period other factors such as microbiolo,gical activity, contaminaevaporation, or water-surface tion, might influence the results. To clucidatc the relationship between dissolved organic compounds aid CaCOR prccipitationr wc collcctcd samples of precipitatcd material periodically during another set of experiments. The Na2COzI solution was added to 8-lo-liter samples of Filtered scawatcr until the pII was 9.5.

ArtificiaI Kancohe Bay ( surface ) Kancohc Bay ( surface ) Coconut Jsland (surface) Lab circulating ( well) Lab circulating ( well) Kaneohc Bay ( surface ) Aquarium ( natural ) Aquarium* ( natural ) Aquarium * (natural)

7.64 8.09 8.14 8.12 7.92, 8.01 8.00 7.94 8.83

5.69 6.65 6.21 5.71 6.10 6.10 5.90 6.10 3.00

0.5

16

1.1
1.2 1.2 1.9 2.0 2.0 2.9

22
261 3x2 GO 48 55 120

3.3, >240< 4.0 >240t

* Various aquaria around the laboratory ganisms in nntural seawater. t Iyo precipitation obscrvcd.

containing

--

or-

Immediately after addition of the Na&O:I, 1 liter of the experimental solution was withdrawn and filtered through a precombusted Gclman type A glass-Fiber filter. The filter was then washed with 5 ml of distilled water. Withdrawal and filtering of 0.5-1.0-l&r aliquots continued at 5-l@ min intervals until the initial seawater samplc was exhausted, or until the CaCO:l prccipitatc was very heavy. The glass-fiber filters were dried over silica gel, and analyzed for CaC03 carbon and organic carbon. WC measured CaCO:$carbon (in a Beckman IR-215 CO2 analyzcr) in the form of CO, rclcascd by treatment with 15% IIaPOL~. Organic carbon was measured as CO2 rcleascd by oxidation with l&$208 after acid treatment. Both reactions took place in the same vesscl. The method is described by Klim (1969). The results of two of these cxpcriments are shown in Fig. 2. Organic carbon is precipitated rapidly from the NazCOR-cn-

chCo3

SATURATION

IN TABLE

SEAWATER

635

1.0-

--0.8 -

NORMAL SEAWATER ORQANIC-RICH SEAWATER

2. Rates of CaCOs nuchtion from Udifida1 seuwater raised to pH 9.5 (clissolved mg-C, 0.5 mg C/liter) 0.1 171.
Na,CO, added/ 100 ml (ml) Time to rapid pH decrease (mj.4

P I

I 0
< 0.6 43 5 z$ % 0 0.4 -

I II 0 II
ARAGONITE \:: I I I

Mg concn (M)

Initial PI-1

<lo* 2.41 x lo- 5.23 x 1O-2

7.891 7.73 7.64

2..81 3.12 5.68

1 8 18

L
i

compounds, comprising about 10% of the total organic carbon, associate with CaCOs nuclei, This association may render the nuclei inactive as sites for further CaCOa Consequently, rapid CaCOn precipitation. precipitation does not occur until these are removed from organic compounds solution.
90

30 TIME,
MIN

60

Effect

of magnesium

FE. 2. Composition of precipitate from NaLIOsenriched seawater as a function of time. Organic carbon is removed from solution before rapid CaC,Os precipitation occurs.

richcd seawaters at the beginning of the expcrimcnts, before the major part of the Organic compounds CaCOs precipitates. may be prccipitatcd because the increased pH causes a decrease in their solubility, or they may be removed from solution by association with the few Ca.C03 nuclei that folrm early in the experiment (Fig. 2.). In either case, organic compounds are rcmoved from solution before rapid CaCOs precipitation occurs. The maximum. amounts of dissolved organic carbon precipitated during the cxperiments arc 0.10 mg C/liter for normal seawater and 0.25 mg C/liter for organicrich ( aquarium) water. This represents about 10% of the initial dissolved organic carbon in these two types of samples. Suess (1970) reported that between 10 and 14% of the dissolved organic carbon in seawater associates with calcite surfaces when the mineral is added to seawater as a fine powder. It is likely that in the expcriments reported here, dissolved organic

Pytkowicz (1965) demonstrated that magncsium in solution influences the rate of In his experiments, C&O3 nucleation. magnesium-free artificial seawater nucleated much faster than natural seawater or magnesium-enriched natural seawater. Pytkowicz did not report the dissolved organic content of theso waters. In an attempt to evaluate the relative importance of magnesium and organics in nucleation inhibition, we did an experiment in which the concentration of dissolved organics was kept constant and the magnesium concentration varied. Magnesium concentrations lower than those in seawater can only be obtained in artificial seawater. Artificial seawaters containing no magnesium, about half the magnesium of seawater, and the magnesium concentrations of seawater (NaCl substituted for MgCl:! to keep the ionic strength constant) were brought to pH 9.5 by addition of 0.1 m Na&O:I solution. The pH change-indicative of prccipita tion-was then monitored. The results are shown in Table 2. The effect of magnesium on CaC03 nucleation is striking. Magnesium at seawater concentration inhibits nucleation from these high plH waters for 18 min. On the other

636
TABLE

KEITH

E.

CHAVl3

AND

ERWIN

SUESS

critical mechanism of inhibition, and the way in which it operates to allow the maintenance of supersaturation in surface seaDissolved CaCl, added (g/100 ml) Mg water, is not obvious. org-C concn 1.25 1.0 1.50 1.75 (mg C/liter) bd Magnesium forms a stable MgCO$ complex in seawater (Garrels, Thompson, and Artificial seawater Siever 1961)) and likewise, many organic <lo N* GYP GYP GYP 0.5 compounds reported in seawater may com2.41 x 1O-2 N GYP GYP GYP 0.5 N GYP GYP 0.5 5.23 x 1O-2 N plcx Ca2+ or COs2- ions. In addition, organic molecules are adsorbed from solution Natural seawater onto CaC03 surfaces in such a way as to ND N N N GYP 1.2 block nucleation sites (Chave and Suess ND N N GYP GYP 1.1 ND N N N GYP 1.2 1967). Each or all of these mechanisms may inhibit the precipitation of CaCOZI *N = none; GYP = gypsum; ND = not determined. from seawater. Supersaturation of surface seawater canhand, Table 1 indicates that under the not be explained solely on the basis of same conditions, dissolved organic matter complexing of Ca2+ or COs2- ions. The in concentrations found in natural seawater degree of supersaturation is lowered by this inhibits nucleation for as long as an hour. process (Garrels and Thompson 1962)) but complexing does not lower the activity of CaCld experiments these ions in seawater below the ion acSolutions of CaC12 can be added to sea- tivity product for calcite. Natural surface water with little change in its pH. Thus, seawater is actually supersaturated, as increasing the CaC03 supersaturation by has been demonstrated by Weyl ( 1961)) addition of CaClz results in quite a differSchmalx and Chave ( 1963), Chave and ent chemical system from Na&Os-enriched Suess ( 1967)) and others. water. Complcxing dots not appear to slow the Samples ( 100 ml) of natural and artifikinetics of ionic interaction to the degree cial seawaters were passed through 0.8-p suggested by Pytkowicz ( KM%), who felt Millipore filters and varying amounts of that it would take 70,000 yr before precipiCaClz solutions were added. Dry CaClz in tation could occur, nor do the experiments amounts ranging from 1.0 to 1.75 g were reported here. Chave and Schmalz (19661) weighed out and dissolved in a minimum of and Chave and Suess (1967) showed that distilled water for addition to the seawater. when sufficient CaC03 nuclei were added The mixtures were stirred continuously fo,r to natural seawater (containing normal magnesium concentrations ) to reduce the 12 hr and watched for precipitate formation. The only solid precipitated in any of effective dissolved organic content through between surface adsorption, equilibration the experiments was gypsum: CaS04*2Hz0 the solid and water occurred within an (Table 3). Calcium carbonate does not precipitate hour. from the calcium-enriched seawaters within The best explanation of the supersatura12 hr. The data perhaps suggest that both tion of surface seawater, based on our data, magnesium and dissolved organic carbon is that CaC03 nuclei are probably forming continuously in natural or Ca2+- o,r COs2-inhibit gypsum nucleation. enriched seawater. The rate of nucleus DISCUSSION formation may be influenced by either disPrecipitation of CaCOs from seawater is solved magnesium or phosphorus (Simkiss inhibited by magnesium in solution, as 1964) or both. The nuclei are inactivated shown by Pytkowicz ( 1965)) and by dis- immediately by adsorption of dissolved orsolved organics, as indicated here. The ganics from solution onto the carbonate

3.

Precipitates formed within 12 hr by addition of CaCL to seawater

C&03

SATURATION

IN

SEAWATER

637

surfaces. This suggestion is in agreement with the observation by Chave and Suess (1967) that the adsorption of dissolved organic matter from seawater onto carbonate surfaces is faster than the precipitation of CaC& onto the same surfaces. Furthermore, in our experiments with enriched seawater, rapid CaC03 precipitation took place only at high pH values, after organics had -been removed from solution (Fig. 2). Finally, inactivated nuclei may account for the CaC03 associated with organic aggregates observed in suspension in shallow and deep ocean water (Wangersky and Gordon 1965 ) . On the basis of this model of carbonate supersaturation in surface seawater, the sea can probably maintain a high degree of supersaturation if pH remains near 8.0, and equilibration will occur only if pH is raised considerably,
REFERENCES

CHAVE, K. E. 1965. Carbonates: Association with organic matter in surface seawater. Science 148 : 1723-1724. -, AND R. F. SCHMALZ. 1966. Carbonatcseawater interaction. Gcochim. Cosmochim. Acta 30: 1037-1048.. -, AND E. SUE!%. 1967. Susncnded minerals in seawater. Trans. N.Y. *Acad. Sci. 2 29 : 991-1000. CLOUD, P. E. 1962. Environment of calcium carbonate deposition west of Andros Island, Bahamas. U.S. Geol. Surv. Prof. Pap. 350. 138 p. GARJTELS, R. M., AND M. E. THOMPSON. 1962. A chemical model for seawater at 25C and

one atmosphere total pressure. Amer. J. Sci. 260 : 57-66. -AND R. SIEVER. 1961. Control of carbonaie solubility by carbonate complexes. Amer. J. Sci. 259: 24-45,. KLIM, D. G. 1969. Interactions between seawater and coral reefs in Kaneohe Bay, Oahu, EIawaii. M.S. thesis, Univ. Hawaii, Honolulu. LYAKIN, Y. I. 1968. Calcium carbonate saturation of Pacific water. Oceanology (USSR) 8: 44-53. McINT~, W. G., AND R. F. PLATFORD. 1964. Dissolved CaCOs in the Labrador Sea. J. Fish. Res. Bd. Can. 21: 1475-1480. MENZEX, D. W., AND R. I?. VACCARO. 1964. The measurcmcnt of dissolved organic and partic. ulate carbon in seawater. Limnol. Oceanogr. 9: 138-142. PYTKOWICZ, R. M. 1965. Rates of inorganic calcium carbonate precipitation. J. Geol. 73: 196-199. -, AND G. A. FOWLER. 1967. Solubility of foraminifera in seawater at high pressures. Geochim. J. 1: 169-182. SCE~LZ, R. F., AND K. E. CIIAVIL 1963. Calcium carbonate: Factors affecting saturation in ocean waters off Bermuda. Science 139 : 1206-1207. %MKISS, K. 1964. The inhibitory effects of some mctabolitcs on the precipitation of CaC03 from artificial and natural seawater. J. Cons., Cons. Perm. Int. Explor. Mer 29: 6-18. SUESS, E. 1970. Interaction of organic compounds with calcium carbonate, Geochim. Cosmochim. Acta 34 : 157-168. WANGERSKY, P. K., AND D. C. GORDON. 1965. Particulate carbonate, organic carbon, and Mn++ in the open ocean. Limnol. Oceanogr,

10: 544-550.

I-I., AND E. TIMMERMAN. 1936. Ober die SSittigung des Seewassers an CaC03, Ann. Hydrogr. Mar. Meteorol. 64: 23-31. WEYL, P. K. 1961. The carbonate saturometer. J. Gcol. 69: 3244.
WA~ENBERG,